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Two families of PVD hard coatings were successfully used for high performance end milling of hardened H13 tool steel. The first family of coatings are AlCrN-based, they are used for wet machining and the other family is based on TiAlCrSiYN coating and are used for dry machining of H13. It was shown that there is a strong potential for further advancement in the wear performance of the coatings by improving the coating architecture as well as by varying the deposition parameters used during their synthesis. A number of deposition parameters of the coatings show a strong impact on wear performance of the cutting tools. Wear performance was related to the structure and a number of nano-mechanical characteristics of the coating layer assessed using the NanoTest system produced by Micro Materials. It was shown that critical characteristics like nano-hardness, loading support factor and nano-scaled scratch resistance can be used to predict the wear performance of a cutting tool. / Thesis / Master of Applied Science (MASc)

Microemulsions are nanostructured dispersions that have unique properties, which make them attractive for applications such as biomaterials, drug delivery, and nanoparticle synthesis. The behaviour of hydrocarbon microemulsions and their applications have been extensively studied, however, there have been very few studies in the preparation or the polymerization of silicone microemulsions. Silicone microemulsions offer a unique template by which to create novel nanoporous silicone elastomers and/or hydrogels. The prevalent use of silicones in biomaterials, coatings, and personal care (to name a few) make the development of silicone-based microemulsions of particular interest. The aim of thesis research was to polymerize silicone microemulsions and to understand the factors that contribute to retaining initial template morphology in the polymeric product. Chapter Two of this thesis focuses on the preparation of silicone microemulsions containing a non-polymerizable and polymerizable trisiloxane surfactant, respectively. Formulations were prepared and characterized by electrical conductivity to determine the microemulsion structure type. Formulations located in the bicontinuous region of the phase diagram were polymerized, producing transparent silicone elastomers. The focus of Chapter Three was to determine the tolerance of silicone microemulsions to selected chemistry that is relevant to silicone polymers. Previous work done in the field of polymerizing silicone microemulsions has been based on radical polymerization processes. There are no reports that examine the polymerization of a silicone microemulsion by room temperature vulcanization (RTV), a common process for creating silicone elastomers. We aimed to better understand the effects of RTV cure on morphology retention from the liquid to polymeric product to determine if this type of chemistry could be used in the formation of nanoporous silicone elastomers either on its own or in conjunction with a radical polymerization process. In order to understand the effects of an RTV process on polymer structure, we examined the effect of the variable components (necessary for the RTV cure) on the silicone microemulsion template. Small angle X-ray scattering (SAXS) and transmission electron microscopy (TEM) were used as tools to characterize materials prior to and after cure. Silicone microemulsions that were cured using the RTV process produced nanoporous polymeric elastomers, however, the initial bicontinuous microemulsion template was not retained. RTV cured microemulsions retained the bicontinuous structure if the RTV cure was preceded by a photopolymerization reaction to “lock-in” surfactant monomers at the oil/water interface. Chapter Four explores the use of silicone microemulsions as a reaction vehicle in the formation of nano-TiO2 particles. The focus of this chapter was the exploitation of microemulsion droplets and bicontinuous structures that were designed to retard TiO2 particle formation in situ. Titanium isopropoxide (TTIP) was incorporated into silicone microemulsions containing varying amounts of water. Interactions between TTIP and the trisiloxane polyether surfactant result in the formation of a compound containing a Ti4+, coordinated to silicone surfactant molecules via a polyether linkage. Titania forms in situ as water is titrated into the surfactant/oil mixture, resulting in the formation of a microemulsion. The formation of TiO2 was monitored by UV-Vis spectroscopy and the TiO2 particles were characterized using transmission electron microscopy. / Thesis / Doctor of Philosophy (PhD) / This thesis is about the chemical modification and polymerization of nanostructured liquids in the form of silicone microemulsions to create nanoporous silicone elastomers (nano is one billionth, 10-9, so 1 nanometer = 1 billionth of meter). Despite the highly prevalent commercial use of silicones and the utility of silicone elastomers, little is known about the polymerization of silicone microemulsions to create nanoporous materials. The first goal of this thesis was to polymerize silicone microemulsions, using methods that have been previously used in the polymerization of hydrocarbon microemulsions. Silicone microemulsions were successfully polymerized using a reactive surfactant and rigidification of the oil phase was achieved using common silicone crosslinking chemistry. The second goal was to understand how the type of chemistry affects changes in structure upon transition from liquid microemulsion to solid polymer. Nanostructuring was retained in polymerized microemulsions both with and without oil phase polymerization. Finally, the third goal was to exploit silicone microemulsion domains to control titanium dioxide particle formation. Particle formation was slowed as a result of domain constricted particle growth.

Pressure injuries cause pain both physically and financially. By creating a comfortable pressure mapping system, pressure injuries can more easily be prevented, and a large expenditure avoided. Nano composite piezo-responsive foam (NCPF) is an inexpensive foam that can be used to measure a static load while still providing a comfortable interface. As NCPF compresses, the impedance changes, correlating to a change in pressure. Optimizing electrode geometry is needed to take full advantage of the impedance change NCPF incurs upon deformation. To optimize electrode geometry, a design of experiment was performed which concluded that a one square inch area of interlaced finger electrodes provides the largest change in impedance with a finger gap of 1.5 mm. The optimized electrode geometry is utilized in several demonstrations including a modular design allowing a wide range of surfaces to be mapped using the same hardware. By building a phenomenological model, NCPF output voltage is converted to pressure readings with an RMSE of 8.02%. This model provides evidence that using NCPF as a pressure sensor is a viable path to creating smart objects that an individual interacts with daily. In addition to the modular design, this technology is demonstrated in pressure sensing gloves and pressure plates, highlighting the feasibility of NCPF as a pressure sensing medium. Each system developed with NCPF is outfitted with an iOS application which allows for real time system feedback as well as record keeping capabilities.

Indianapolis / In this thesis, cellulose nanofiber (CNF) reinforced polylactic acid (PLA) filaments were produced for 3D printing applications using melt extrusion. The use of CNF reinforcement has the potential to improve the mechanical properties of PLA, making it a more suitable material for various 3D printing applications. To produce the nanocomposites, a master batch with a high concentration of CNFs was premixed with PLA, and then diluted to final concentrations of 1, 3, and 5 wt% during the extrusion process. The dilution was carried out to assess the effects of varying CNF concentrations on the morphology and mechanical properties of the composites. The results showed that the addition of 3 wt.% CNF significantly enhanced the mechanical properties of the PLA composites. Specifically, the tensile strength increased by 77.7%, the compressive strength increased by 62.7%, and the flexural strength increased by 60.2%. These findings demonstrate that the melt extrusion of CNF reinforced PLA filaments is a viable approach for producing nanocomposites with improved mechanical properties for 3D printing applications. In conclusion, the study highlights the potential of CNF reinforcement in improving the mechanical properties of PLA for 3D printing applications. The results can provide valuable information for researchers and industries in the field of 3D printing and materials science, as well as support the development of more advanced and sustainable 3D printing materials.

Magnetic nano-clusters in silicon involving iron and cobalt were synthesized using low energy (50 keV) ion implantation technique and post-implantation thermal annealing. Before the irradiation, multiple ion-solid interaction simulations were carried out to estimate optimal ion energy and fluence for each experiment. For high-fluence low-energy irradiation of heavy ions in a relatively lighter substrate, modeling the ion irradiation process using dynamic code SDTrimSP showed better agreement with the experimental results compared to the widely used static simulation code TRIM. A saturation in concentration (~ 48%) profile of the 50 keV Fe or Co implants in Si was seen at a fluence of ~ 2 × 1017 ions/cm2. Further study showed that for structures with a curved surface, particularly for nanowires, better simulation results could be extracted using a code "Iradina" as the curve geometry of the target surface can be directly defined in the input file. The compositional, structural, and magnetic properties were studied using Rutherford backscattering spectrometry, X-ray photoelectron spectroscopy, X-ray diffraction, atom probe tomography, and vibrating sample magnetometry. Irradiation of high-current (~ 2 μA/cm2) 50 keV Fe ions into Si at a fluence of 2 × 1017 ions/cm2 showed the formation of Fe5Si3 nano structures in the near-surface region of the substrate. Post-implantation thermal annealing in vacuum at 500 οC for one hour showed a significant enhancement in structural and magnetic properties. Similar high-current irradiation of 50 keV Co with a fluence of 3.2 × 1016 ions/cm2 into Si substrate showed the formation of superparamagnetic structure even at room temperature in the as-implanted samples. The simulation results for irradiation of Co and Fe on the curved surface were validated by ion irradiation on pre-fabricated Si nano tip followed by atom probe tomography analysis.

A cheaper access to space is needed in current times and new technologies need to be developed to reduce the cost of space access to increase productivity. This thesis presents a study on carbon fiber reinforced polymer (CFRP) composites which is an enabling technology for cost reduction in space vehicles. A literature review of the behavior of CFRP composite has been conducted and it was found that the currently used IM7/977 carbon fiber reinforced epoxy composites do not microcrack at a lower number of thermal cycles. Nano-composites and Thermoplastic matrix composites have been found as two promising alternatives for cryogenic applications. With the use of nano sized inclusions in currently used epoxy resins, coefficient of thermal expansion can be reduced while increase in strength and fracture toughness can be achieved. Some thermoplastics were found to have non-linear stress-strain relationships with signs of ductility even at 4.2K. Both of these resin systems show promise in reducing microcracking at cryogenic temperatures.

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